Copolymers of halfesters of maleic anhydride and -alkoxypropene

ABSTRACT

Alkylene oxide monoether halfesters of maleic anhydride/2alkoxypropene copolymers and alkyl and alkylene oxide mixed halfesters of said copolymers are homogeneous film-forming compositions useful in hair spray preparations. These halfesters are prepared by the esterification of the maleic anhydrive/2alkoxypropene copolymer with an appropriate alcohol.

United States Patent 1 Schlumbom et al.

5]March 20, 1973 COPOLYMERS OF HALFESTERS OF MALEIC ANHYDRIDE ANDALKOXYPROPENE ln i'en ior sz Peter Schlumbom; lrvington;

David A. Gordon, Scarsdale, both of NY.

Assigne: Ciba-Geigy timiara'iidn, Ardsiey,

Filed: 7 Jan. 8,1971

Appl. No.: 105,081

Related US. Application Data Division of Ser. No. 888,832, Dec. 29,1969, Pat. No. 3,635,916.

US. Cl. ..260/78.5 T, 252/857, 260/334 R, 260/785 R, 424/47, 424/70,424/DlG. I

int. Cl. ..C08i 29/38 Field of Search ..260/78.5 R, 78.5 T, 33.4 PQ;424/70, DIG. l, DIG. 2, 47

[56] References Cited UNITED STATES PATENTS 3,342,787 9/1967 Muskat..260/78.5

Primary Examiner-James A. Seidleck Assistant Examiner-John Kight, IllAttorney-Karl F. Jorda et a1.

[57] ABSTRACT 3 Claims, No Drawings wherein R is an alkyl group havingfrom one to four carbon atoms and R is an alkylene oxide monoether groupof the general formula:

wherein n is an integer from 2 to 4 inclusive,

m is an integer from I to 20 and R" is an alkyl group containing fromone to 18 carbon atoms.

A further embodiment of this invention also includes mixtures ofalkylene oxide monoether halfesters described above and alkyl halfesterswherein the alkyl group is from one to eight carbon atoms. The resincompositions comprising the mixed halfesters can contain from 2 and 100weight per cent of the alkylene oxide monoether halfesters and from to98 weight per cent of the alkyl halfesters.

The instant resins are useful as the main components in leathertreatment systems and in hair sprays. For the leather treatmentcompositions halfesters prepared from the low molecular weightcopolymers are preferred. In the hair spray compositions the halfestersof this invention are particularly useful as the film forming component.For this purpose the halfesters prepared from both the lower and thehigher molecular weight copolymers can be employed. The mixed halfestersare advantageously employed in hair spray formulations when the maleicanhydride/2alkoxypropene copolymer is of a lower molecular weight.Generally the low molecular weight copolymers have the intrinsicviscosities of up to about 0.12 and the higher molecular weightcopolymers have the intrinsic viscosities of about 0.2 and higher. Theintrinsic viscosity is measured at 30C in tetrahydrofuran.

The maleic anhydride/2-alkoxypropene copolymer which is converted to thehalfester can be prepared by a method described in the copendingapplication of Okamura et al., Ser. No. 842,328, filed July 16, I969.The copolymer prepared by this method generally is of lower molecularweight having an intrinsic viscosity of up to about 0.1. Copolymershaving higher intrinsic viscosities can be prepared by the addition of2- methoxypropene to the reaction mixture as described in Example 2 ofthis application. Copolymers prepared by this method have intrinsicviscosities of up to about 0.45.

In general, the halfesters of the above polymers are prepared by heatingand agitating the maleic anhydride/Z-alkoxypropene copolymer with eitheran ether alcohol or mixture of ether alcohol and an alkyl alcohol. Saidalcohol or alcohol mixtures can be employed either in equimolar amountsor in excess with reference to the maleic anhydride. The reactiontemperature is in the range of from about 50 to about C. The process canbe carried out either in the presence or absence of both an inertsolvent and an acid catalyst. Under these conditions only a halfester isformed. Illustrative examples of aliphatic alcohols that can be employedin preparing the mixed halfester copolymers are methanol, ethanol,propanol, isopropanol, butanol, hexanol, octanol and the like. Examplesof ether alcohols include 2-methoxyethanol; 2- ethoxyethanol;2-butoxyethanol; 2-hexoxyethanol; diethylene glycol methyl, ethyl,propyl, butyl and hexyl ether; triethylene glycol methyl ether;triethylene glycol butyl ether; methoxy polyethylene glycols such asCarbowax 350 or 750 (manufactured by Union Carbide), polyethylene (20)stearyl ether; propylene glycol butyl ether; dipropylene glycol methylether and the like.

If an alcohol is used in an equimolar amount then it is preferable tocarry out the reaction in an inert solvent. Suitable solvents which canbe used are solvents having an effective boiling point of at least 50Cwhich include ketones like acetone, methyl ethyl ketone, ethers liketetrahydrofuran, dioxane or aromatics such as toluene, ethylbenzene,xylene and the like.

The acid catalysts that can be employed in preparing the halfesters arethe mineral acids and the aromatic sulfonic acids. Illustrativeexamples'of the mineral acids are sulfuric acid, hydrochloric acid,sulfonic acid, phosphoric acid, and the like. Illustrative examples ofaromatic sulfonic acids are benzene-sulfonic acid, toluenesulfonic acid,xylenesulfonic acid, 5-nitro-l,3- benzenedisulfonic acid,1,3-benzenedisulfonic acid, 1,3,5-benzenetrisulfonic acid,naphthalenesult'onic acid, anthracenesulfonic acid and the like.

As noted above, the halfester copolymers of this invention can be usedas the film forming component in hair spray compositions. The filmsformed from the hair sprays have generally good adhering properties andgood flexibility in addition to good curl retention properties in humidweather. The copolymers can also be employed as leather treating agents.

To illustrate further the nature of this invention there are presentedbelow the following examples. Examples 1 to 4 illustrate the preparationof the maleic anhydride/2-alkoxypropene copolymers and Examples 5 to 9illustrate the preparation of the halfesters of said copolymers.

EXAMPLE I 2.5 parts of maleic anhydride and 0.2 parts of a,aazo-bis-isobutyronitrile were added to 46.7 parts of acetone dimethylketal. The mixture was reacted for 20 hours at 60 to obtain 3.54 partsof copolymer. The product, a copolymer of maleic anhydride and 2-methoxypropene was a white powdery material which had the intrinsicviscosity of 0.1 in tetrahydrofuran at 30C.

1f, instead of 46.7 parts acetone dimethyl ketal, 50 parts of acetonediethyl ketal, 50 parts of acetone dipropyl ketal or 55 parts of acetonedibutyl ketal are used and otherwise is proceeded in the same way, the1:1 copolymers of maleic anhydride and the akoxy alkenes derived fromthe mentioned ketals are obtained.

EXAMPLE 2 EXAMPLE 3 When in Example 2 the quantities of 2-methoxypropeneand acetone dimethyl ketal were 0.54 and 13.3 parts respectively, 2.1parts of the copolymer were obtained. The intrinsic viscosity was 0.16.

EXAMPLE 4 When in Example 2 acetone dimethyl ketal was replaced by 7.9parts of 1,4-dioxane, 2.57 parts of the copolymer were obtained. Theintrinsic viscosity was EXAMPLE 5 11.9 parts of maleicanhydride/2-methoxypropene copolymer of an intrinsic viscosity of 0.1and 31.5 parts of 2-ethoxyethano1 were stirred in a nitrogen atmospherefor hours at 110C. The polymeric halfester was separated by pouring thereaction mixture into diethyl ether. After drying, 12.1 parts of2-ethoxyethyl halfester of maleic anhydride/2-methoxypropene copolymerwere obtained as an almost colorless white powder. The material readilydissolves in ethanol.

EXAMPLE 6 When in Example 5 maleic anhydride/2-methoxypropene copolymeris replaced with 14.9 parts of maleic anhydride/2-butoxypropenecopolymer, a 2- ethoxyethanol halfester of the starting copolymer inExample 5 is obtained.

EXAMPLE 7 When in Example 5, 2'ethoxyethanol is replaced with 31.5 partsof 3-ethoxypropano1, a 3-ethoxypropanol halfester of maleicanhydride/Z-methoxypropene copolymer is obtained.

EXAMPLE 8 Ten parts of maleic anhydride/2-methoxypropene copolymerhaving an intrinsic viscosity of 0.1, 10.4 parts of Brij 78 apolyethylene monostearyl ether manufactured by Atlas ChemicalIndustries, Inc., 2.3

parts of ethanol, 0.2 parts of concentrated HCl and 16 parts of methylethyl ketone were stirred at a reflux temperature in a nitrogenatmosphere for 10 hours. The polymeric halfester was separated bypouring the reaction mixture into diethyl ether. After drying, 123 partsof the mixed halfesters of maleic anhydride/2- methoxypropene copolymercontaining Brij 78 and ethanol groups as the alcohol component wereobtained.

EXAMPLE 9 When in Example 8 ethanol was replaced with 3.7 parts ofn-butanol, 12.7 parts of the mixed halfesters of maleicanhydride/Z-methoxypropene copolymer containing Brij 78 and n-butanolgroups as the alcohol component were obtained.

EXAMPLE 10 Preparation of Hair Spray Composition 7.9 parts2-ethoxyethanol halfester of maleic anhydride/2-methoxypropene copolymerhaving an intrinsic viscosity at 30C in tetrahydrofuran of 0.24 and 0.14parts triisopropanolamine were dissolved in 52 parts of anhydrousethanol. The polymer solution was sprayed with an aerosol dispenser on aswatch of human hair which was then combed and set to a curl. Afterdrying a thin transparent non-gummy film formed on the hair whichprovided a high curl retention. On washing with warm water and soap orconventional shampoo preparations the film was easily removed.

Similar results are obtained with formulations containing halfestercopolymers mentioned below:

1. Methyl diethylene glycol halfester prepared from maleicanhydridel2-methoxypropene copolymer having an intrinsic viscosity at30C in tetrahydrofuran of 0.1.

2. l-lexyl diethylene glycol halfester obtained from maleicanhydride/2-methoxypropene copolymer with an intrinsic viscosity at 30Cin tetrahydrofuran of 0. 1.

3. Methyl diethylene glycol halfester of maleicanhydride/Z-butoxypropene copolymer.

4. Mixed halfester obtained from maleic anhydride/Z-methoxypropenecopolymer having an intrinsic viscosity at 30C in tetrahydrofuran of0.1, n-butanol and methoxy polyethylene glycol of a molecular weight ofabout 750 as the alcohol component in a molar ratio of 9.5 to 0.5.

5. Mixed halfester obtained from maleic anhydride/Z-methoxypropenecopolymer having an intrinsic viscosity of 30C in tetrahydrofuran of0.1, n-butanol and methoxy triethylene glycol in a molar ration of 1:2.

6. A halfester copolymer as described in Example 8.

What is claimed:

1. A hair spray composition containing in solution as the film formingcomponent a halfester copolymer having the repeating unit of the formulawherein R is an alkyl group having up to four carbon atoms and R is analkylene oxide monoether group or a mixture of alkylene oxide monoetherand alkyl group having up to eight carbon atoms, said alkylene oxidemonoether group having the formula wherein n is an integer from 2 to 4inclusive, m is an integer from 1 to 20 and R" is an alkyl groupcontaining from one to 18 carbon atoms. 2. A hair spray composition ofclaim 1 wherein the halfester copolymer is a mixedn-butanol/polyethylene

2. A hair spray composition of claim 1 wherein the halfester copolymeris a mixed n-butanol/polyethylene glycol methyl ether halfester ofmaleic anhydride/2-methoxypropene copolymer wherein the molecular weightof said glycol is about
 750. 3. A hair spray composition of claim 1wherein the halfester copolymer is a mixed ethanol/polyethylene glycolmonostearyl ether halfester of maleic anhydride/2-methoxypropenecopolymer wherein the glycol monostearyl ether has a molecular weight ofabout 1150.